Acid azo dyestuffs for wool containing chromium and process for the manufacture of same



Patented Apr. 20, 1926.

UNITED STATES PATENT OFFICE.

HERMANN FRITZSCHE, HANS GUBLER, AND FRITZ STRAUB, F BASED, SWITZERLAND,ASSIGNORS TO THE SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASED,

SWITZERLAND.

ACID AZO DYESTUFFS FOR WOOL CONTAINING CHROMIUM AND PROCESS FOR THEMANUFACTURE OF SAME.

No Drawing.

To all 707mm it may concern:

Be it known that we, HERMANN Fm'rzsoHE,

A I-lANs GUBIJ'IR, and Farm STRAUB, all citizens of the Swiss Republic,and residing at Basel, Switzerland, have invented new and useful AcidAzo Dyestuffs for W001 Containing Chromium and Process for theManufacture of Same, of which the folloW-' ing is a full, clear, andexact specification.

The present invention ,relates to dyestuffs containing chromium whichform valuable acid azo coloring'matters for W001. It comprises theproduction of the dyestufi's, the dyestuffs themselves, as well as thedyed fabrics or other materials, dyed with the new dyestuffs.

It has been found that by combining diazotized aromaticortho-hydroxy-diazo compounds which contain no nitrocups, withamino-compounds of the napht alene series which are capable of beingcoupled in orthoposition to the amino-group, new dyestuffs are obtained.These dyestuffs however, are of no value as such or as mordantdyestufi's, but they will yield valuable acid dyestuffs when treatedwith agents adapted to yield chromium.

The new acid azo dyestuffs for W001 are therefore the complex chromiumcompounds of the dyestuffs of the general formula: R-N:N-R' wherein R-signifies a hydroxylated aromatic nucleus which contains no nitro-group,and in which the azo-bridge adheres to an ortho-position in respect ofthe hydroxyl-group, and R an aminonaphthalene-compound in which theazobridge adheres to an ortho-position in respect of the amino-group.They form blackish powders, the aqueous solutions of which in a thinlayer appear blue and in a thicker er violet. They dye wool in an acidbath hie-green to deep olive-green tints of excellent fastness. Theydiffer from the products obtained from nitrated diazo com- 4 pounds bybetter properties, especially enhanced fastness to milling.

It has been found that the az o-dyestuflfs Application filed October 15,1923. Serial No. 668,764.

in question can be made in such manner that one molecule of thediazo-com ound is caused to react on one molecule of t e amine.

It has further been found that by coupling ,B-naphthylamine it isadvantageous to employ two molecules of ,B-naphthylar'nine forExample 1. 189 parts of 2-amino-1-phenol-4-sulfonic and are diazotizedin the usual manner.

The diazo solution is carefully neutralized with sodium carbonate andadded, with constant stirring, to a hot :1 ueous solution of 359 partsof ,B-naphthylamme hydrochloride. Stirring is continued at highertemperature,

for instance between 4085 C. until cou-- pling is complete. Thecrystalline reaction product which separates, consisting of a doulecompound of the ortho-amin0-azo-dyestuff and fl-naphthylamine, istreated with cold caustic soda solution. The ,B-naphthylamine is thuseliminated and, after filtration, an orange solution is obtained fromwhich the pure ortho-amino-azo-dyestufi may be separated by salting out.It dissolves in water to an orange solution, and dyes wool in an acidbath orange tints which by after-chroming become green.

35 parts of this dyestufi are dissolved in 350 parts of boiling water.The solution is mixed with a solution of chromium formate correspondinwith 11.4 parts of Cr O and the mixture is boiled for a long time in {areflux apparatus. It is then in part evaporated and the chromiumcompound is salted V. 4; chloro -2 -amino 1 -pheno1- 6 -sulfonic out byadding common salt. \Vhen dried it forms a dark powder, the aqueoussolutions of which in a thin layer appear blue and in a thicker layerviolet. It dyes wool in an acid bath full deep green tints. By usinganother agent adapted to yield chromium, such as for instance, chromiumacetate, chromium fluoride, or hydrated chromium hydroxide, likedyestuffs are obtained.

Emam'ple 2.

mon salt. This dyestufi' dissolves in water to a yellowish-red solutionand dyes wool in an acid bath red-orange.

46.6 parts of this dyestutf are dissolved in 800 parts of boiling water;the solution is mixed with an excess of a freshly precipitated paste ofhydrated chromium hydroxide and the mixture is boiled for a longtime ina reflux apparatus. The unaltered hydrated chromium hydroxide isfiltered and the clear filtrate evaporated to dryness. The chromiumcompound thus obtained forms a dark powder, the aqueous solutions ofwhich in a. thin layer appear blue and in a thicker layer violet. Itdyes wool in an acid bath deep, covered, blue-green tints.

The following table shows the main properties of some of thedyestiii'fsa'nd chromium compounds obtainable according to the inventionDiem-component.

. B-or a-naphthylamine derivative.

1. .-chloro-2-amino-I-phenol II. 4-chloro-2-amino-I-phenol III.4-chloro-2-emin0-1-phenol-5-sulionic acid. IV.2-amino-1-plieno1-4-sulionic acid acid. VI.e-methyl-2-amino-1-phenol'5-su1fonic acid.VILfii-chloro-2-amino-1-phenol-5-su1ionic aci2-amlnonaphthalene-o-sulfonic acid 2-eminonaphthalene-5,7-disultonieacid. w-methanesulfcnic acid of fi-naphthyl mine. fl-naphthylam nefi-naphthylamine fi-naphthyl amine 1-aminonaphthalene-4-sultonic acid A-d tufi.

Z0 yes Chromiumcopnpmfmd-I Color of the Color otwool c0 or? aqueoussoludyed in acid g tion. baths a Orange Reddish-yellow. Dark-greenOrange Orange Dark-green e- Reddish-orangc. Yellow-red" Blue-greenOrange..- Dark-green Orange.-- Blue-green Orange. Orange. Dark-greenOrange Orange Dark-green The formula of the dyestufi No. I is:

OH NH: I ON: 8

The formula of the dyestufi No. II is:

The formula of the dyestufi NoVIV is:

OK 11TH: O 8 801K manufacture of new acid azo d The formula of thedyestuir' No. VII is:

OH NH:

What we claim is 1. As a new process the herein described estufis forW001 containing chromium, which consists in con ling thediazo-eoinpounds of aromatic orthoydroxy-amino-compounds whichcontain'no nitro-groups, with amino-compounds of the naphthalene seriesof being coupled in ortho-position to the amino-group, and then treatingthe dyestufi's thus obtained with trivalent compounds of chromium.

2. As a new process the herein described I manufacture of new acid azodyestufis for W001 containing chromium, which consists in con hug thediazo-compounds of aromatic orthoydroxy-amino-compounds which con-- tainnonitro-groups, with B-naphthylamine which are capable v compounds andthen treating the dyestuffs thus obtained with trivalent compounds ofchromium. I

3. As' a new process the herein described manufacture of new acid azodyestufl's for wool containing chromium, which consists in coupling thediazo-compounds of sulfonated aromatic ortho hydroxy amino compoundswhich contain no nitro-groups, with B-naphthylamine compounds, and thentreating the dyestuffs thus obtained with trivalent compounds ofchromium.

4. As a new process the herein described u'ianufacture of new acid azodyestuffs for W001 containing chromium, which consists in coupling thediazo-compounds of sulfonated aromatic ortho hydroxy amino compoundswhich contain no nitro-groups, with ,B-naphthylamine, and then treatingthe dyestuffs thus obtained with trivalent compounds of chromium.

5. As a new process the herein described manufacture of new acid azodyestufls for wool containing chromium, which consists in coupling onemolecule of the diazo-compound of a sulfonated aromaticortho-hydroxy-amino-compound, which contains no nitro-groups, with twomolecules of ,B- naphthylamine, then eliminating the ,8- naphthylaminefrom the obtained double compound of the azo-dyestuff and ,B-naphthylamine, and finally treating the dyestuft' thus obtained withtrivalent compounds of chromium.

6. As a new process the herein described manufacture of new acid azodyestuffs for wool containing chromium, which consists in coupling onemolecule of the diazo-compound of an ortho-aminophenolsulfonic acid withtwo molecules of ,B-naphthylamine, then eliminating the ,B-naphthylaminefrom the obtained double compound of the azodyestufi andB-naphthylamine, and finally treating the dyestufl' thus obtained withtrivalent compounds of chromium.

7. As a new process the herein described manufacture of new acid azodyestuffs for W001 containing chromium, which consists in coupling onemolecule of the diazo-compound of the 1-hydroxybenzene-2 amino-4-sulfonic acid with two molecules of ,B- naphthylamine, theneliminating the ,B

naphthylamine from the obtained double compound of the azo-dyestuff and,B-naphthylamine, and finally treating the dyestuff thus obtained withtrivalent compounds of chromium.

, 8. As new products the herein describedacid azo dyestufl's for woolwhich are the complex chromium compounds of the azo dyestuffs of thegeneral formula RN= N-R' wherein R signifies a hydroxylated aromaticnucleus which contains no nitrogroups, and in which the azo-bridgeadheres to an ortho-position in respect of the OH- group, and R -auamino-naphthalene compound in which the azo-bridge adheres to anortho-position in respect of the aminogroup, which compounds formblackish powders, the aqueous solutions of which in athin layer appearblue and in a thicker layer violet, and which dye wool in an acid bathblue-green to deep olive-green tints of excellent fastness.

9. As new products the-herein described acid azo dyestuffs for woolwhich are the complex chromium compounds of the azo dyestuffs of thegeneral formula R-N= N-R wherein R signifies a hydroxylated aromaticnucleus which contains no nitrogroups, and in which the azo-bridgeadheres to an ortho-position in respect of the OH- group, and R aQ-amino-naphthalene compound in whichthe azo-bridge adheres toposition-1, which compounds form blackish powders, the aqueous solutionsof which in a thin layer appear blue and in a thicker layer violet, andwhich dye wool in an acid bath bluereen to deep olive-green tints ofexcellent astness.

10. As new products the herein described.

acid azo dyestuffs for wool which are the complex chromium compounds ofthe azo dyestuffs of the general formula RN= N-R wherein R signifies ahydroxylated and sulfonated aromatic nucleus which contains nonitro-groups, and in which the azo-bridge adheres to an ortho-positionin respect of the OH-group, and R a 2-amin0 naphthalene compound inwhich the azobridge. adheres to position-1, which compounds formblackish powders, the aqueous solutions of which in a thin layer appearblue and in a thicker layer violet, and which dye wool in an acid bathblue-green to deep olive-green tints of excellent fastness.

11. As new products the herein described acid azo dyestuffs for woolwhich are the complex chromium compounds of the azo dyestuffs of thegeneral formula R-N= N-R' wherein R signifies a hydroxylated andsulfonated aromatic nucleus which contains no nitro-groups, and in whichtheazobridge adheres to an ortho-position in respect ofthe OH-group, andR an unsulfonated Q-amino-naphthalene compound in which the azo-bridgeadheres to position-1, which compounds form blackish powders, theaqueous solutions of which in a thin layer appear blue and in a thickerlayer violet, and which dye wool in an acid bath blue-green to deepolive-green tints of excelacid 'azo (lyeslulf for wool which are thecomplex chromium compounds of the azo dyestufl 0f the formula:

slozfi which compound forms a blackish powder,

HE MANN FRITZSCHE. HANS GUBLER. FRITZ STRAIN).

